Integrally Waterproofed Concrete

ABSTRACT

An exemplary composition for enhancing water repellency in cementitious material comprises a hydrophobic material solute that is dissolved in a glycol ether solvent. Thus, the composition is provided in the form of a non-aqueous solution or emulsion wherein water is in a noncontinuous phase. The use of such compositions to modify cementitious compositions and the cementitious materials obtained thereby are also described.

FIELD OF THE INVENTION

The present invention pertains to additives and admixtures forhydratable cementitious compositions, and more particularly to additivesand admixtures for imparting water repellant properties to cementitiouscompositions.

BACKGROUND OF THE INVENTION

It is known to incorporate water repellant materials into hydratablecementitious materials such as cement pastes, masonry cements, mortars,and concrete to achieve a degree of moisture impermeability. Acementitious composition which is impermeable to water and dampness,ideally, may not require the application of externally applied moisturebarriers such as bituminous coatings or waterproofing membranelaminates.

In U.S. Pat. 6,761,765 B2 (issued Jul. 13, 2004), Lu disclosed anemulsion admixture for imparting water repellant properties to cements.The admixture comprised a polymer, a surfactant, and hydrophobicmaterial in the form of organic esters of aliphatic carboxylic acid. Thepolymer was preferably a latex polymer (e.g., styrene butadienecopolymer latex). The surfactant could include any surfactant capable ofemulsifying the hydrophobic material, and most preferably was anethoxylated nonylphenol. Lu theorized that mixing the emulsifiedhydrophobic material into the cementitious composition would evenlydistribute it throughout the cementitious matrix as well as over itssurface. This purportedly prevented water from entering and exitingporous cementitious structures such as blocks, pavers, and retainingwall units (See Col. 4, 11. 17-24).

Emulsified hydrophobic materials, however, were long known and usedpreviously. For example, U.S. Pat. Nos. 3,865,601 and 3,885,985disclosed additives comprising oil-in-water emulsions that contained awater-insoluble, water-repelling acid component (e.g., tall oil, anemulsifier (e.g., a salt of such an acid)) and a setting time retardingagent (e.g., sucrose). As explained in the background of U.S. Pat. No.5,108,511, this additive was dispersible in water form so that the riskof overdosing could be minimized. Further, the additive was provided ina form that allowed additional optional components, such asair-entraining agents, to be included. An improved emulsion additive, asdescribed in U.S. Pat. No. 4,375,987, further included an emulsionstabilizer (e.g., a glycol). The stabilizer, as is now well known,prevents oil-in-water emulsions from breaking down when exposed tofreezing temperatures during shipping or storage. (See e.g., U.S. Pat.No. 5,108,511 at column 2, lines 11-23).

In U.S. Pat. No. 5,108,511, Wiegland observed that oil-in-wateremulsions were unusable when they broke down. Even when stabilizers(such as glycol) were used in such aqueous systems, the emulsion couldbreak down due to extreme temperature fluctuation and long term thermalcycling. Thus, for the express purpose of increasing workability,plasticity, and board life in mortar cement, Wiegland proposed anadditive that comprised a salt of stearic acid (e.g., calcium stearate,aluminum stearate), a set retarding carbohydrate, an ethylenic glycolselected from mono-, di-, tri-, and tetraethylene glycols, and celluloseether. The stearic salt was saponified by heating the stearic acid andlime powder.

The use of oil-in-water emulsions and saponified metal salts (e.g.,calcium stearate) has been commercialized in the industry for some time.An emulsion-based, water-repellancy enhancer, added during theintergrinding process for making cement from clinker, is commerciallyavailable from Grace Construction Products, Cambridge USA, under thetradename HYDROPHOBE®. A calcium stearate suspension, provided in theform of finely ground calcium stearate powder, dispersed in an aqueouscarrier, is commercially available from Grace under the tradenameDARAPEL®.

To improve upon the prior art water repellency technology, the presentinventors propose to avoid the use of aqueous emulsions or aqueoussolvents.

SUMMARY OF THE INVENTION

The present invention provides a novel composition for enhancing waterrepellency in cement, masonry cement, concrete, and other cementitiousmaterials. In many cases, it is hoped that the moisture permeability insuch cementitious materials can be lowered to the point at which anexternally-applied waterproofing coating or membrane is eliminated,thereby achieving a reduction of materials and labor expense.

Novel compositions of the invention may be combined with a cement orcementitious material such as concrete, either as an additive (e.g.,during intergrinding of clinker to produce cement) or admixture (e.g.,to finished cement, mortar, or concrete) in a liquid-dispensible form.This favors accurate, controllable, verifiable dosage amounts.

Exemplary compositions of the invention comprise: a solute portionhaving at least one hydrophobic material operative to enhance waterrepellency in a cementitious material; and a non-aqueous solvent portionhaving at least one glycol ether, which is preferably operative toinhibit drying shrinkage in a cementitious material; said solute andsolvent being present in said composition in a ratio of 95:5 to 5:95;said solute and solvent portions being mixed uniformly together in theform of a nonaqueous solution or in the form of an emulsion whereinwater is present as a non-continuous phase. It is preferred that thehydrophobic material be non-air-entraining and non-saponified.

Because compositions of the invention are not intended to achieveoil-in-water emulsions, but rather are intended to be used in the formof nonaqueous solutions or emulsions wherein water is present only as anon-continuous phase, the use of surfactants can be avoided. Surfactantsoften entrain too much air when used in mortars and concretes. Althougha certain amount of air, when distributed as fine micro-bubbles, canbestow freeze-thaw durability to mortars and concretes, air levels whichare too high may lead to passageways by which moisture can penetrate. Itis believed that the present invention provides better air levelmanagement in cementitious materials without requiring that defoamers beadded.

The present invention allows certain conventional hydrophobic materialsto be employed for use in modifying cementitious compositions, and thesewould include materials that are preferably non-air-entraining innature. This may be accomplished by dissolving the hydrophobic materialsdirectly in a non-aqueous liquid carrier, one that preferably comprisesone or more shrinkage reducing admixtures, such as certain glycolethers, as will be further discussed hereinafter.

This combination of solute and non-aqueous solvent results in a largertemperature stability range, and eliminates the need for heated storagein colder environments. This is a tremendous advantage when comparedwith prior art water repellant systems that were based on conventionalemulsions or aqueous suspensions.

For example, exemplary hydrophobic materials believed to be suitable foruse in the present invention include an aliphatic carboxylic acid orsalt or ester thereof, a fatty acid or salt or the ester thereof, anatural or synthetic wax, a natural or synthetic oil, a siliconecompound, a silane compound, a siloxane compound, a naphthalenecompound, a melamine compound, a dicarboxylic acid or the salt thereof,or a mixture of any of the foregoing.

Especially preferred hydrophobic materials (solute) contemplated for usein the invention include fatty acids such as butyl stearate, butyloleate, or a mixture thereof; while preferred glycol ethers (solvent)include di(oxypropylene)glycol-t-butyl ether (DPTB),di(oxypropylene)glycol-n-butyl ether (DPNB), or a mixture thereof. Thesolvent may additionally include a low molecular glycol such asdi(oxypropylene)glycol (DPG), di(oxyethylene)glycol (DIEG), or mixturethereof.

A further detailed description of exemplary solutes (hydrophobicmaterials) and solvents (such as glycol ethers) is provided hereinafter.

By avoiding the use of a large water portion, the compositions of theinvention will realize several advantages. First, manufacturers canavoid the additional step required for making the aqueous emulsion ordispersion as well as the costs of surfactants and stabilizers. Further,the cost of shipping water that constitutes the bulk of the aqueousemulsion or suspension will be decreased. Furthermore, with little or nowater content, the compositions of the invention will be less hospitableto bacteria and other microorganisms.

In further exemplary compositions of the invention, one or more combpolymer superplasticizers, such as poly(oxyalkylene) types as known inthe art, may be additionally incorporated to lower the water-to-cementratio and improve workability or fluidity of the cementitiouscomposition. While such superplasticizers may involve a small amount ofwater, it is nevertheless preferred that compositions of the inventionbe substantially devoid of water, e.g., less than 35% and morepreferably less than 15% by total volume.

The present invention also concerns methods for enhancing waterrepellency in cementitious materials, and also concerns cementitiousmaterials containing the above-described water repellency enhancingcompositions. Other advantages and features of the invention aredescribed hereinafter.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

The inventive compositions of the invention, as previously described,are useful as additives or admixtures for modifying cements andcementitious compositions and materials. The present invention thus alsopertains to cementitious materials and methods for enhancing waterrepellency in them.

The terms “cementitious composition” or “cementitious material” as maybe used herein, sometimes interchangeably, include and refer to not onlyto “cements” but also to pastes (or slurries), mortars, and grouts, suchas oil well cementing grouts, shotcrete, and concrete compositionscomprising a hydraulic cement binder. The terms “paste”, “mortar” and“concrete” are terms of art: pastes are mixtures composed of ahydratable (or hydraulic) cement binder (usually, but not exclusively,Portland cement, Masonry cement, Mortar cement, and/or gypsum, and mayalso include limestone, hydrated lime, pozzolans such as fly ash and/orgranulated blast furnace slag, metakaolin, rice hull ash, and silicafume or other materials commonly included in such cements) and water;“mortars” are pastes additionally including fine aggregate (e.g., sand),and “concretes” are mortars additionally including coarse aggregate(e.g., crushed rock or gravel). The cementitious materials described inthis invention are formed by mixing required amounts of certainmaterials, e.g., a hydraulic cement, water, and fine and/or coarseaggregate, as may be required for making a particular cementitiouscomposition.

In addition, the term “cement” may also include and refer to calciumaluminate cement, hydratable alumina, hydratable aluminum oxide,colloidal silica, silicon oxide, magnesia, in addition to Portlandcement and pozzolans as just mentioned above.

The water-to-cement (W/C) ratio used in making cast or spray-appliedcementitious mixtures is not believed to be critical to achievingoptimal water repellency properties, although a suitable W/C ratio couldbe from about 0.25 to about 0.60. It is desirable to minimize the amountof water needed so as to consolidate, and to avoid deformities in, thestructure formed by the cementitious mixture.

When used as admixtures for modifying cement, concrete, or othercementitious material, the compositions of the invention may be combinedwith hydratable cement binder material before, during, or after additionof water. Alternatively, the inventive compositions can be added as aninterground additive during the manufacturing process wherein clinker istransformed into hydratable cement.

Exemplary compositions of the invention may be generally described asnon-aqueous solutions having at least one solute and a non-aqueoussolvent present in a ratio of 95:5 to 5:95, and, more preferably, 70:30to 30:70. Preferably, the solute and solvent portions are mixeduniformly together to form a non-emulsion liquid solution. Morepreferably, the solute may be present in the composition in an amount of70 to 30 percent based on total dry weight solids in the composition;while the solvent may be present in an amount of 30 to 70 percent basedon total weight of the composition.

Exemplary hydrophobic materials contemplated for use in the inventioninclude but are not limited to aliphatic carboxylic acid or salt orester thereof, a fatty acid or salt or the ester thereof, a natural orsynthetic wax, a natural or synthetic oil, a silicone compound (silane,siloxane), a naphthalene compound, a melamine compound, a dicarboxylicacid or the salt thereof, or a mixture thereof. The most preferredhydrophobic materials which are by themselves non-air-entraining whenincorporated into hydratable cementitous compositions. Where thehydrophobic material is incorporated into the solvent in solid form, itis preferable to ground the material as finely as possible to facilitatedissolving of the solute into the solution.

Among the preferred hydrophobic materials, therefore, are aliphaticcarboxylic acids, salts, or esters thereof, and in particular theorganic (e.g., aliphatic) esters of these carboxylic acids or salts.Preferably, the organic ester of an aliphatic carboxylic acid isrepresented by the general formula R₁-R₂, wherein R₁ is C₁₂-C₁₈aliphatic carboxylic acid ester, and R₂ is a linear or branched C₁-C₁₀alkyl. Preferred aliphatic carboxylic acid esters include, but are notlimited to, stearate, oleate, naturally occurring oils (e.g., coconutoil, castor oil, tall oil fatty acid), laurate, palmitate, myristicester, linoleic ester, and salts and/or mixtures thereof.

Preferred hydrophobic materials include, but are not limited to, alkylstearate esters, alkyl oleate esters, and mixtures thereof. Preferably,the organic ester of a stearate has the general formula C₁₇H₃₅COOR₃ andthe organic ester of an oleate has the general formulaCH₃(CH₂)₇═(CH₂)₇COOR₄, wherein R₃ and R₄ are each independently a linearor branched C₁ to C₁₀ alkyl. A preferred stearate is butyl stearate, anda preferred oleate is butyl oleate. In particularly preferrednon-air-entraining hydrophobic materials, both butyl oleate and butylstearate are used together.

More generally speaking, exemplary compositions of the inventioncomprise at least one hydrophobic material such as a stearate, anoleate, a laurate, a palmitate, a myristic ester, a linoleic ester, acoconut oil, a castor oil, tall oil fatty acid, or a salt thereof, or amixture thereof. Preferably such hydrophobic material isnon-air-entraining when incorporated into cementitious materials (e.g.,cement mortars and concretes). Preferably, hydrophobic material is analkyl stearate ester, an alkyl oleate ester, or mixture thereof. Morepreferably, the hydrophobic material is butyl oleate (BO), butylstearate (BS), or a mixture of these two, which may be used in a ratio(BO:BS) of 5:1 to 1:5; more preferably, in a ratio of 4:1 to 1:2; and,most preferably, in a ratio of 3:1 to 1:1.

Exemplary hydrophobic materials may also include fatty acids as well astheir salts. For example, calcium stearate and zinc stearate may beused, and these are commercially available (both in powder form) fromNORAC, Inc. Another example is tall oil fatty acid (TOFA) which isavailable from Grace Construction Chemicals, Cambridge, USA, under thetradename RX-901.

Exemplary hydrophobic materials may also include natural waxes, such asparaffinic wax, ceresin wax, and beeswax. Exemplary synthetic waxes mayalso be used. For example, such waxes are commercially available fromDow Chemicals under the tradename Carbowax®.

Exemplary hydrophobic materials may also include naturally occurringoils (e.g., coconut oil, castor oil), some of these being already notedabove, as well as synthetic oils.

Other exemplary hydrophobic materials are silicones, silanes, andsiloxanes. For example, butyltrimethoxysilane and other silanes arecommercially available from Dow Corning. A wide range of organosiliconcompounds are available as well from Dow Corning.

Still further exemplary hydrophobic materials believed to be suitablefor purposes of the invention include naphthalene compounds (e.g., bisisoproponyl naphthalene, calcium di(naphthalene) sulfonate), and alsomelamine compounds.

Another exemplary hydrophobic material is a dicarboxylic acid or thesalt thereof. Such materials will have the chemical formulaR²OOC—C(R¹)(H)—(CH₂)_(n)—COOR³wherein R¹ is a C₁₂ to C₁₈ alkyl or alkylene group; R² and R³ arehydrogen or a cation (e.g., sodium, potassium, lithium, zinc, butyl),and “n” is an integer from 1 to 6. A preferred dicarboxylic salt isdi-sodium salt of tetrapropenyl butandediodic acid, having the formulaNa⁺⁻OOC—C(C₁₂H₂₃)(H)—CH₂—COO⁻Na⁺For example, a 20% solution of this dicarboxylic salt (“DSS”) can bemixed into a glycol ether solvent as follows: 45% DPTB, 450% DPG, 2%DSS, and 8% water (wherein “DPTB” representsdi(oxypropylene)glycol-t-butyl ether and “DPG” representsdi(oxypropylene)glycol.

Exemplary glycol ether solvents believed to be suitable for use in theinvention comprise (i) an oxyalkylene glycol; (ii) an oxyalkylene etheradduct of an alcohol, glycol, or glycerol; or (iii) a mixture thereof.Exemplary oxyalkylene glycols which are believed to be suitable for usein the present invention can be represented by the formula HO(AO)_(n)Hwherein: A represents a C₂-C₄ alkylene group (such as ethylene,propylene, butylenes, and the like, along with mixtures thereof, withethylene and propylene being most preferred); O represents an oxygenatom, and n represents an integer of from 1 to about 30, and morepreferably 1-3. The AO groups in a particular glycol molecule may be thesame or may be different. Examples of such glycols include diethyleneglycol, dipropylene glycol, tripropylene glycol,di(ethoxy)(di(propoxy)glycol and the like. Further glycols may includepolyalkylene glycols(poly(oxyalkylene)glycols) having molecular weightsup to about 1200. The AO groups forming the chain of such glycols maycontain a single type of alkylene ether group or a mixture of alkyleneether groups which may be in block or random arrangement. Examples ofthe oxyalkylene glycols are polypropylene glycol, polyethylene glycol,poly(oxyethylene)(oxypropylene)glycol and the like.

Exemplary oxyalkylene adducts of monoalcohols which are believed to besuitable for use in the invention can be represented by the formulaRO(AO)_(m)H wherein R is a hydrocarbon group, such as a C₁-C₇ alkyl or aC₅-C₆ cycloalkyl group; A represents a C₂-C₄ alkylene group, Orepresents an oxygen atom and m represents an integer of from 1 to about10. Examples of such R groups are methyl, ethyl, propyl, isopropyl,n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, cyclopentyl, cyclohexyland the like. The preferred R groups are C₃-C₅ alkyl such as n-propyl,isopropyl, n-butyl, t-butyl and the like. In various embodiments of theinvention, is preferred that the R groups be the same. A is a C₂-C₄(preferably C₂-C₃) alkylene group, such as ethylene, propylene and thelike and mixtures thereof in the same chain, and m is an integer of from1 to about 10, preferably 2or3.

In preferred embodiments, the solvent isdi(oxypropylene)glycol-tertiary-butyl ether (“DPTB”),di(oxypropylene)glycol-n-butyl ether (“DPNB”), or a mixture thereof,optionally with di(oxypropylene)glycol (“DPG”), di(oxyethylene)glycol(DEIG), or mixture thereof.

Exemplary compositions of the invention therefore comprise at least onehydrophobic material which could include a stearate, an oleate, anaturally occurring oil, a laurate, a palmitate, a myristic ester, alinoleic ester, or a salt thereof, or a mixture thereof; and a glycolether solvent which could include (i) an oxyalkylene glycol; (ii) anoxyalkylene ether adduct of an alcohol, glycol, or glycerol; or (iii) amixture thereof. In most preferred compositions, the at least onehydrophobic material comprises butyl oleate and butyl stearate, and theglycol ether solvent is DPTB, DPNB, or a mixture thereof, optionallywith low molecular weight DPG or DIEG. These solvents are especiallypreferred because they have excellent shrinkage and air detrainingcapabilities when incorporated into hydratable cementitious mixtures.Hence, preferred solvents are operative to detrain air in cementitiousmaterials.

Further exemplary compositions of the invention may comprise at leastone comb polymer superplasticizer, as conventionally used in theindustry, for improving plasticity, workability, and/or slump as may bedesired. Most preferred are comb polymer superplasticizers havingpendant poly(oxyalkylene) groups. Such plasticizers are generally known.A suitable superplasticizer is commercially available from Grace underthe tradename ADVA®. Superplasticizers can be incorporated intocompositions of the invention, preferably after the solute(s) andsolvent are mixed thoroughly together, in an amount of 5 to 30 percentbased on total weight of the composition. Poly(oxyalkylene)superplasticizers may contain a small amount of water as a result offormulation or manufacture. However, it is preferable that the totalamount of water not exceed 30% by total volume of composition, and morepreferably not exceed 5% by total volume of composition.

Preferably, the compositions of the invention are substantially devoidof surfactants, or other surface active agents, as would normally beotherwise required to form emulsion systems. Thus, the use of a metalsalt (e.g., sodium, potassium, lithium) of a fatty acid or tall oilfatty acid is less preferred due to the tendency of such metal salts toentrain air when incorporated into cementitious materials; and thus, ifcertain metal salts are used as hydrophobic materials, it may beadvisable to employ an air-detraining agent.

Exemplary methods of the invention therefore include modifying acementitious material by introducing to a hydratable cementitiousmaterial the above-described water repellency enhancing compositions. Aspreviously mentioned, these can be incorporated as additives during themanufacture of cement from clinker, or as admixtures incorporated intothe finished cement, mortar, concrete, or other cementitious mixture.

The following examples are provided for illustrative purposes.

EXAMPLE 1

Several solutions of the invention were produced by dissolving anorganic ester of an aliphatic acid, or an aliphatic carboxylic acid,into glycol ether. These resulted in transparent solutions as confirmedby shining a laser through the liquid. (According to Tyndall, a solutionwill not scatter the laser beam, whereas an emulsion or dispersionwill). Unlike emulsions, these solutions are stable at a hightemperature of 46 degrees C. and will revert to a solution if takenbelow solidification temperature and melted. In addition, viscosities atlow temperatures are well below the 250 cP criterion needed for pumpingwith standard admixture pumps. The data is presented in Table 1 below.Sample 1 shows the benefit of using DPNB and DPG to reduce the freezingpoint of butyl oleate (“BO”) and butyl stearate (“BS”) blends. TABLE 1At 2° C. 5° C. % Components Viscosity Viscosity 46° C. Sample DPNB DPGBO BS Form (cP) Form (cP) Form 1 38 21 20.5 20.5 HS* — HL** 21 HL 2 3821 27.3 13.7 HL 23.8 HL 20.1 HL 3 38 21 30.75 10.25 HL 23.7 HL 20.5 HL 40 0 67 33 HS HL 5 29.5 29.5 20.5 20.5 HS HL HL 6 29.5 29.5 27.3 27.7 HLHL HL 7 33 33 17 17 HL HL HL 8 33 33 22.7 11.3 HL HL HL*HS = Homogeneous solid/gel;**HL = Homogeneous liquid solution;DPNB = dipropylene glycol n butyl ether;DPG = dipropylene glycolBO = butyl oleate;BS = butyl stearate

EXAMPLE 2

An exemplary additive of the invention, wherein a hydrophobic materialwas dissolved in a glycol ether shrinkage reducing solvent to obtain theadditive, was shown to enhance moisture impermeability of concretesamples. This enhanced impermeability was confirmed in terms of reducingwater absorption, shrinkage, and electrical conductivity, in comparisonto concrete samples not containing the additive.

The improvements are seen in concretes having high water-to-cementratios (w/c) as well as lower w/c ratios which are typical of lesspermeable concretes. Table 2 shows typical improvements in the BritishAbsorption Test (BS 1881 Part 122) for composition 1, 2 and 3 from Table1 denoted as “IWC1,” “IWC2,” and “IWC3.” This is a key test forevaluating admixtures for achieving integral waterproofing ofcementitious compositions, and numbers of about 1% or less areconsidered excellent.

The data suggests that IWC mixes had better workability with lowersuperplasticizer levels than shrinkage reducing admixture (SRA) usedalone (Mixture 10), and had reduced absorption levels when compared toSRA used alone, and showed a 25% improvement at two-thirds dosage. TABLE2 Polycarboxylate Final Superplasticizer Slump British Mixture (oz/cwt)*Air (%) (in)** UW (pcf) Absorption %  1. Control 0.5w/c 2.5 4 8.00 151.72.8515  2. Control 0.4w/c 6 2.4 7.00 151.7 1.8487  3. WC1/@.5gpy 6 1.77.50 158.9 0.9925  4. IWC1/@.075gpy 6 1.7 7.25 158.5 0.9819  5.IWC1/@1gpy 5.5 1.8 4.00 157.8 0.9266  6. IWC2/@0.5gpy 6 1.4 7.25 159.01.0174  7. IWC3/@0.5gpy 6 1.5 7.25 158.5 0.9439  8. IWC2/@0.75gpy 8 1.77.50 158.1 0.9338  9. IWC3/0@0.75gpy 6.5 1.7 6.50 158.2 0.9715 10. 50%DPNB/ 12 2.4 4.00 156.4 1.2618    50% DPG@0.75gpy*The polycarboxylate Superplasticizer was Grace Construction Productsbrand available under the tradename Adva ®.**Slump is an indication of workability and is measured using thestandard slump cone technique, and values shown were found to be between4 and 8 inches which is desirable for normal concretes used in flooringand wall applications.

EXAMPLE 3

Properties for various mixes produced using IWC1, SRA, and damp-proofingmaterials such as calcium stearate emulsion (Grace Darapel® brand),butyl oleate, and butyl stearate. The damp-proofing materials have aminor effect on drying shrinkage. As shown in Example 2 above, the SRAdoes not reduce water absorption as well as the IWC samples.

Synergy was surprisingly discovered by dissolving the hydrophobicmaterial or materials in a shrinkage reducing admixture (SRA) solventbefore addition to cement or concrete, because the combined additiveallowed for lower overall component dosages in comparison to separateuse of hydrophobic material and separate use of the SRA.

Furthermore, less air was created in the concrete than was the case withseparately added damp-proofing components. This is beneficial forinterior flooring applications.

Permeability of concrete samples was measured using methodology similarto that described in ASTM C 1202. Current across the ends of acylindrically shaped concrete sample having a 4-inch diameter by 12-inchlength was measured at 60 Volts DC after one minute. Higher currentscorrespond to concretes having higher permability to water and moisture.It is noted that reducing the water/cement ratio of the concrete from0.5 to 0.4 had a major effect, and the addition of calcium stearate byitself showed little improvement. However, the concrete mixtures havingthe IWC additives of the invention showed a significant drop. It wasfound that although the hydrophobic material or the shrinkage reducingadmixtures (SRA), when used separately, could match or exceed some ofthe qualities of the IWC samples of the invention, the IWC samples usedless overall material and achieved favorable reductions in absorption,permeability, and shrinkage all across the board. TABLE 3 ASTM C157Drying Shrinkage 28 Current (mA) days drying 1- (Modified ASTM day curein Air C1202) at 12 days Mix # Mixture BSI Abs. mold (%) wet curing04353-1 Control 0.5w/c 2.83 0.0675 2.5 69.2 04353-2 Control 0.4w/c 1.842.4 45.3 04353-3 Control 0.4w/c 1.0 galDarapel 0.96 0.0465 2.7 43.604353-4 Control 0.4w/c 1.5 galDarapel 0.73 0.0535 2.9 44.1 04353-5IWC1@.5gpy 1.08 0.042 1.9 37.245 04353-6 IWC1@.75gpy 0.98 0.040 1.537.455 04353-7 IWC1@1gpy 0.90 0.036 1.5 34.68 04353-8DPNB/DPG50/50)@1gpy 1.20 0.0315 1.9 38.94 04353-9 50/50BO/BS@0.5gpy 0.820.0515 1.7 37.535

EXAMPLE 4

Other hydrophobic solute materials that can provide excellent propertiesare naphthalenes, e.g., Ruetasolv DI, which is C₁₆H₂₀, Naphthalene,bis(1-methylethyl)-(9Cl). When added at 1:2 to 2:1 to 50% dipropyleneglycol t-butyl ether/50% dipropylene glycol, the naphthalene formed aclear solution as confirmed by laser light test, and was also found tobe soluble in IWC2 (See Formula 2 in Table 1). Properties of concretesamples made using these materials, compared to control samples, areshown in Table 4. Reducing the water-to-cement (w/c) ratio slightlyimproved initial capillary absorption (Si) as measured using ASTM C1585. However, there was a significant reduction in Si when additives ofthe invention were employed, as well as a significant decrease inshrinkage (in comparison to samples wherein w/c ratio was merelylowered). TABLE 4 28-day Current (mA) shrinkage (Modified after ASTMC1202) Si (mm- 7 days moist at 28 days Formulation w/c s^(−1/2)) curing(%) wet curing 1. Control 1 0.5 30.5 0.0335 55.6 2. Control 2 0.4 26.50.0245 33.9 3. 25% DPTB/25% 0.4 10.5 0.0075 34.3    DPG/    50%Ruetasolv 4. 66.7% DPNB/ 0.4 10.0 0.0145 31.6    33.3% RUETASOLV

EXAMPLE 5

Stable non-oil-in-water emulsions were made using glycol ether toprovide a continuous liquid phase and a naphthalenesulfonic acid as thehydrophobic material. An exemplary hydrophobic material was NaCorr®which is a tradename for naphthalenesulfonic acid, dinonyl-calcium salt(C₂₈H₄₄O₃S.½Ca)). This additive, when employed in a concrete sample,provided benefits in terms of reducing shrinkage and absorption. Laserlight tests confirmed that these formulations are emulsions in at leasta range of 1:2 to 2:1 mass ratio to the glycol ether. They did notfreeze or separate at temperatures from −5 to +46 degrees Celcius.Shrinkage and absorption data of samples containing the hydrophobicagent in a glycol ether shrinkage reduction agent (SRA), using an SRAavailable from Grace Construction Products under the tradename ECLIPSE®are summarized in the table below. TABLE 5 Shrinkage at Capillary 28days (7-day Absorption* Formulation wet cure) % C_(ab) (g/m²-s^(1/2)) 1.Control 0.029 13.3 2. Eclipse (1.5 gpy) 0.014 10.8 3. 25% DPTB/25%DPG/50% NaCorr 0.0165 8.93Note all concrete at 0.45 w/c.*3-inch × 3-inch cylinders dried at 70° C., cooled to 21° C., and placedin water at 21° C.

EXAMPLE 6

A wide range of formulations of the invention was tested to demonstratethat formed stable solutions or non-oil-in-water emulsions could beprovided. The combinations, which are provided for illustrative purposesonly and are not inclusive of all potential combinations realizable fromthe present disclosure, are identified in Table 6 below. TABLE 6Components (%) Stearic Stable Solution (S) Formula DPNB DPG BO BS DPTBRuetasolv NaCorr Acid or Emulsion (E) 1 33.3 33.3 33.4 E 2 16.7 16.766.6 E 3 25 25 50 E 4 16.7 16.7 66.6 S 5 25 25 50 S 6 33.3 33.3 33.4 S 766.6 16.7 16.7 S 8 66.7 30 3.3 S 9 38 21 20.5 20.5 S 10 38 21 27.3 13.7S 11 38 21 30.75 10.25 S 12 38 21 41 0 S 13 34.2 18.9 24.6 12.3 10 S 1434.2 18.9 24.6 12.3 10 S 15 34.2 18.9 18.45 18.45 10 S 16 46.75 46.756.5 S 17 47.5 23.75 23.75 5 S

EXAMPLE 7

Further exemplary hydrophobic materials were into DPTB and DPG. Thesehydrophobic materials included tall oil fatty acid (TOFA), a metal saltof a fatty acid (e.g., zinc stearate), and a wax (e.g., polyethyleneglycol, about 200 molecular weight, available from Dow Chemical asCARBOWAX). TOFA (50%) was blended with DPTB (25%) and DPG (25%) formed astable mixture at room temperature, percentages based on weight). Zincstearate (5.6%) was blended with DPTB (47.2%) and DPG (47.2%) and alsoprovided a stable mixture at room temperature. The wax (33.4%) wasblended with DPTB and DPG each at 33.3%, and provided a stable mixtureat room temperature.

EXAMPLE 8

A further exemplary stable solution of the invention was made bycombining a hydrophobic material, polyethylene glycol (PEG) havingapproximately 1000 molecular weight, in di(oxypropylene)glycol-t-butylether (DPTB) and di(oxypropylene)glycol (DPG), in the following ratio:47.15% DPTP, 47.15% DPG, and 5.7% PEG. The PEG was commerciallyavailable from DOW under the tradename CARBOWAX 1000.

EXAMPLE 9

A still further exemplary stable solution of the invention was made bydissolving a 20% solution of di-sodium salt of tetrapropenylbutandediodic acid, having the formula Na⁺⁻OOC—C(C₁₂H₂₃)(H)—CH₂—COO⁻Na⁺into DPTB and DPG, such that the final solution had the followingcomponents: 45% DPTB, 45% DPG, 2% DSS, and 8% H₂O. Another solution wasmade and also found to be stable, and this had the following components:35% DPTB, 35% DPG, 6% DSS, and 24% H₂O. It is believed that increasingthe amount of the hydrophobic material, without using the aqueoussolution (so that no water would be introduced into the solution), wouldalso work.

EXAMPLE 10

A still further exemplary stable solution of the invention was made byincorporating a silane (e.g., i-butyltrimethoxysilane from Dow Corningunder the tradename Z-2306) in solvent, as follows: 29.4% DPTB, 29.4%DPG, and 41.2% Z-2306. This rendered a clear solution at roomtemperature

The foregoing examples and exemplary embodiments are provided forillustrative purposes and are not intended to limit the scope of theinvention.

1. A composition, comprising: a solute portion having at least onehydrophobic material operative to enhance water repellency in acementitious material; and a non-aqueous solvent portion having at leastone glycol ether operative to inhibit drying shrinkage in a cementitiousmaterial; said solute and solvent being present in said composition in aratio of 95:5 to 5:95; said solute and solvent portions being mixeduniformly together in the form of a nonaqueous solution or in the formof an emulsion wherein water is present as a non-continuous phase. 2.The composition of claim 1 wherein said hydrophobic material isnon-air-entraining when incorporated into a hydratable cementitiouscomposition.
 3. The composition of claim 1 wherein said hydrophobicmaterial is non-saponified.
 4. The composition of claim 1 comprisingwater in an amount of 0-30% based on total volume of said composition.5. The composition of claim 1 wherein said composition is devoid ofwater.
 6. The composition of claim 1 wherein said solute and solvent ispresent in said composition in a ratio of 70:30 to 30:70.
 7. Thecomposition of claim 1 wherein said at least one hydrophobic materialsolute comprises an aliphatic carboxylic acid or salt thereof.
 8. Thecomposition of claim 7 wherein said at least one hydrophobic materialsolute comprises an aliphatic ester of an aliphatic carboxylic acid orsalt thereof.
 9. The composition of claim 1 wherein said at least onehydrophobic material is an organic ester of an aliphatic carboxylic acidrepresented by the general formula R₁-R₂, wherein R₁ is C₁₂-C₁₈aliphatic carboxylic acid ester, and R₂ is a linear or branched C₁ toC₁₀ alkyl.
 10. The composition of claim 9 wherein said at least onehydrophobic material solute comprises a stearate, an oleate, a naturallyoccurring oil, a laurate, a palmitate, a myristic ester, a linoleicester, coconut oil, castor oil, or a salt or a mixture thereof.
 11. Thecomposition of claim 9 wherein said at least one hydrophobic materialsolute comprises an alkyl oleate ester, an alkyl stearate ester, ormixture thereof.
 12. The composition of claim 9 wherein said at leastone hydrophobic material solute comprises butyl oleate, butyl stearate,or a mixture thereof.
 13. The composition of claim 12 wherein saidsolute comprises a butyl oleate and a butyl stearate.
 14. Thecomposition of claim 13 wherein said butyl oleate and butyl stearate arepresent in said composition in an amount no less than 30 percent and inan amount no greater than 50 percent based on dry weight total solids insaid composition.
 15. The composition of claim 1 wherein said at leastone hydrophobic material comprises: an aliphatic carboxylic acid or saltor ester thereof, a fatty acid or salt or the ester thereof, a naturalor synthetic wax, a natural or synthetic oil, a silicone compound, asilane compound, a siloxane compound, a naphthalene compound, a melaminecompound, a dicarboxylic acid or the salt thereof, or a mixture thereof.16. The composition of claim 1 wherein said glycol ether solventcomprises (i) an oxyalkylene glycol; (ii) an oxyalkylene ether adduct ofan alcohol, glycol, or glycerol; or (iii) a mixture thereof.
 17. Thecomposition of claim 16 wherein said glycol ether solvent comprises (i)di(propylene)glycol-tertiary-butyl ether, di(propylene)glycol-n-butylether, or a mixture thereof; and (ii) optionally di(oxypropylene)glycol,di(oxyethylene)glycol, or mixture thereof.
 18. The composition of claim1 wherein said at least one hydrophobic material solute comprises astearate, an oleate, a naturally occurring oil, a laurate, a palmitate,a myristic ester, a linoleic ester, or a salt or a mixture thereof; andsaid glycol ether solvent comprises (i) an oxyalkylene glycol; (ii) anoxyalkylene ether adduct of an alcohol, glycol, or glycerol; or (iii)mixture thereof.
 19. The composition of claim 1 wherein said at leastone hydrophobic material comprises butyl stearate and butyl oleate, andsaid at least one glycol ether solvent comprises (i)di(oxypropylene)glycol-t-butyl ether, di(oxypropylene)glycol-n-butylether, or a mixture thereof; and optionally (ii) optionallydi(oxypropylene)glycol, di(oxyethylene)glycol, or mixture thereof. 20.The composition of claim 15 wherein said at least one hydrophobicmaterial is a dicarboxylic acid or salt having the formulaR²OOC—C(R¹)(H)—(CH₂)_(n)—COOR³ wherein R¹ is a C₁₂ to C₁₈ alkyl oralkylene group; R² and R³ are hydrogen or a cation, and “n” is aninteger from 1 to
 6. 21. The composition of claim 1 wherein said atleast one solvent is operative to detrain air in hydratable cementitiouscompositions.
 22. The composition of claim 1 further comprising at leastone comb polymer superplasticizer.
 23. The composition of claim 22wherein said at least one comb polymer superplasticizer comprisespoly(oxyalkylene) groups, and said comb polymer superplasticizercomprises water in an amount of 0-30% by total volume of saidcomposition.
 24. The composition of claim 1 further comprising water inan amount not exceeding 5% by total volume of said composition.
 25. Thecomposition of claim 1 which is devoid of a surfactant.
 26. Thecomposition of claim 1 which is devoid of an air entraining metal fattyacid.
 27. Method for modifying a cementitious material comprisingcombining with a hydratable cementitious binder the composition ofclaim
 1. 28. A cementitious material containing the composition of claim1.